Catalytic process



United States Patent CATALYTIC PROCESS NoDrawiug. Application May 21, 1954 Serial No. 431,579

12 Claims. (Cl. 260-943) This invention relates to a process for the conversion of ethylene to normally solidresinous, wax-like and grease-like hydrocarbon products by contact with a catalytic mixture prepared by admixing an alkali metal aluminum hydride having the general formula MAIH; wherein M represents an alkali metal, with a catalyst comprising essentially nickel oxide extended on an active carbon such as an active coconut charcoal.

One object of our invention is to provide novel and i highly useful catalytic mixtures for the preparation of high molecular weight polymers from ethylene-containing gas mixtures. Another object is to provide a relatively low-temperature, low-pressure process for the polymerization or interpolymerization of ethylene in substantial yields to form high molecular weight normally solid polymeric materials having molecular weights ranging upwardly from 300. These and other objects of our invention will become apparent from the following description thereof.

Briefly, the inventive process comprises the conversion of ethylene in substantial yields to high molecular weight polymers having a molecular weight of at least 300 and including grease-like, wax-like and tough, resinous ethylene polymers, by contacting ethylene with a catalytic mixture prepared by admixing an alkali metal aluminum hydride having the general formula MAlH wherein M represents an alkali metal, with a solid catalyst comprising essentially a 'nickel oxide-activated carbon containing a minor proportion, usually between about 0.1 and about 20 weight percent, of nickel oxide (calculated as nickel) and a major proportion of activated carbon, preferably a coconut charcoal. The catalyst will be'hereinafter referred to as the nickel catalyst.

j The contacting of ethylene, nickel catalyst and alkali 1 metalv aluminum hydride is effected at temperatures erably about 100C. to about 150C. It is highly desirable to supply to the reaction zone a liquid medium which serves both as a reaction medium and a solvent for the solid reaction products. Suitable liquid reaction media for polymerization include various hydrocarbons, such as liquid saturated hydrocarbons or an aromatic hydrocarbon such as benzene, toluene or xylenes. The conversion of ethylene or other feed stock can be efiected in the absence of a liquid reaction medium and the catalyst containing accumulated solid polymeric conversion products can be treated from time to time, within or outside the conversion zone, to effect removal of conversion products therefrom and, if necessary, reactivation or regeneration of the catalyst for further use. The ethylene partial pressure in the reaction zone can be varied between about atmospheric pressure and 15,000 p.s.i.g. or even higher pressures, but is usually effected at pressures between about 200 and about 5000 p.s.i., or most often at about 1000 p.s.i.

The practice of the process of the present invention leads to ethylene polymers of widely variant molecular weight ranges and attendant physical and mechanical within the. range of about 25 C. to" about 250C, prefa properties, dependent upon the selection of operating conditions. The inventive process is characterized by extreme flexibility both as regards operating conditions and as regards the products producible thereby. Thus the present process can be effected over extremely broad ranges of temperature and pressure. The practice of the present process can lead to grease-life ethylene homo polymers having an approximate molecular weight range of 300 to 700, wax-like ethylene homopolymers having an approximate specific viscosity x10 between about 1000 and 10,000, and tough, resinous ethylene homopolymers having an approximate specific viscosity (x10 of 10,000 to more than 300,000

[(1 relative -1) X10 By the term tough, resinous polyethylene as used herein, we mean polymer having a brittle point below -50C. (A.S.T.M. method D74651T), impact strength greater than two foot pounds per inch of notch (A.S.T.M. method D256-47T-Izod machine) and minimum elongation at room temperature (C.) of 100%.

Ethylene may be polymerized alone or in the presence of propylene or other mono-olefinic hydrocarbons such as n-butytlenes, isobutylenes, t-butylethylene; acetylene, butadiene, isoprene, and the like, usually in proportions between about 1 and about 25% by weight, based on the weight of ethylene.

An important feature of the present invention is employment of the aluminohydride of an alkali metal, viz. lithium, sodium, potassium, rubidium or cesium. we prefer to use the aluminohydrides of Li, Na and K. We may employ the alkaline earth metal aluminohydrides in lieu of or together with alkali metal aluminohydrides. The inclusion of the alkali metal aluminum hydride with the nickel catalyst results in increased yields of solid polymers of ethylene.

An efiective proportion of alkali metal aluminum hydride promoter is employed in our process, e.g., from about 0.01 to about 1 part by weight per part by weight of nickel catalyst (total weight of solid catalyst) although the ratio may be 2 or even more. Usually, We employ about 0.1 to about 0.5 part by weight of alkali metal aluminum hydride per part by weight of the supported nickel catalyst. The optimum proportions can readily be detemined in specific instances by simple small-scale tests with the specific feed stocks, liquid reaction medium, reaction medium; catalyst ratio, catalyst, temperature, pressure and nature of the product which is desired.

The nickel component of the catalyst is'extended upon a major proportion of an activated carbon. Thus, we may employ activated charcoals derived from cellulosic materials, particularly coconut, having surface areas between about 700 and about 1200 square meters per gram, pore volumes of about 0.53 to 0.58 cc. per gram and pore diameters of about 20 to A., and, in some instances, small amounts of combined oxygen. The activated charcoal or other carbon support may be pretreated with nitric acid before use as a catalyst support in order to remove basic materials, for example, as described in E. F. Peters application for United States Letters Patent, Serial No. 164,825, filed May 27, 1950, now U.S.P. 2,692,295.

The preparation of nickel catalysts supported upon activated carbon, particularly coconut charcoal, is well known in the art and the preparative methods form no part of the present invention. Usually we prefer to prepare the catalyst be a cheap, simple and eflicacious technique, which is described briefly hereinafter.

A suitable method of catalyst preparation involves adsorbing nickel nitrate from an aqueous solution upon a porous active carbon such as a suitable charcoal in .3 an amount sufficient to produce the desired nickel content in the finished catalyst. The charcoal containing adsorbed nickel salt is thenv treated thermally at temperatures between about 200 and about 350 C. to effect decomposition of nickel nitrate to form nickel oxide, suitably by heating under a partial vacuum such as l to 20 mm. of mercury (absolute pressure) or in the presence of steam or by the application of heat, vacuum and steam, as is known in the art. The resultant catalyst comprises principally nickel oxide extended upon charcoal.

' Although the nickel catalyst may contain between about 0.1 and about 20 weight percent of nickel (calculated as metallic nickel), we usually employ catalyst containing between about 3 and about 10 weight percent of nickel. The activated carbon support seems to play a unique role in the catalyst. Other supports which might be considered prima facie equivalents, greatly reduce or virtually destroy the power of the catalyst to produce solid polymers from ethylene, viz. alumina and silica supports such as kieselguhr.

If it is desired to employ the nickel catalyst in the form of pellets large enough to be retained on a 20- mesh sieve or at least about 0.1 inch in the largest dimension, it is desirable to pellet the nickel catalyst with between about 50 and about 95 weight percent, based on the total weight of the pellet, of a diflicultly reducible metal oxide filler material such as alumina, titania, zirconia or silica.

The nickel catalyst can be employed in various forms and sizes, e.g., as powder, granules, microspheres, broken filter cake, lumps, or shaped pellets. A convenient form in which the catalysts may be employed is as granules of about 20-100 mesh/ inch size range.

Although ethylene may be polymerized to produce normally solid polymers in the presence of alkali metal aluminum hydride-nickel oxide-charcoal catalysts even at room temperature, we prefer to employ temperatures between about 75" C. and about 150 C.

Reaction pressures may be varied within the range of about 15 p.s.i. ethylene partial pressure to the maximum ethylene partial pressure which can economically be employed in suitable commercial equipment, for example up to as much as 30,000 p.s.i. A convenient ethylene partial pressure range for the manufacture of solid polymers by the use of the present catalyst is about 200 to about 10,000 p.s.i., which constitutes a distinct advantage over the commercial high pressure ethylene polymerization processes which apparently require operating pressures in the range of about 20,000 to about 50,000 p.s.i.

The charging stock to the present polymerization process preferably comprises essentially ethylene. The ethylene charging stocks may contain inert hydrocarbons, as in refinery gas streams, for example, methane, ethane, propane, etc. However, it is preferred to employ as pure and concentrated ethylene charging stocks as it is possible to obtain. It is desirable to minimize or avoid the introduction of oxygen, carbon dioxide, water or sulfur compounds into contact with the catalyst.

The contact time or space velocity employed in the polymerization process will be selected with reference to the other variables, catalysts, the specific type of product desiredand the extent of ethylene conversion desired in any given run or pass over the catalyst. In general, this variable is readily adjustable to obtain the desired results. In operations in which the olefin charging stock is caused to flow continuously into and out of contact with the solid catalyst, suitable liquid hourly space velocities are usually selected between about 0.1 and about 10 volumes, preferably about 0.5 to 5 or about 2 volumes of olefin solution in a liquid reaction medium, which is usually an aromatic hydrocarbon such as benzene or xylenes; tetralin or other cycloaliphatic hydrocarbon,

such as cyclohexane or decalin (decahydronaphthalene).

employed as a liquid The amount of ethylene in such solution may be in the range of about 2 to 50% by weight, preferably about 2 to about 10 weight percent or, for example, about 5 to 10 weight percent. When the ethylene concentration in the liquid reaction medium is decreased below about 2 weight percent, the molecular weight and melt viscosity of the polymeric products tend to drop sharply. In general, the rate of ethylene polymerization tends to increase with increasing concentration of the ethylene in the liquid reaction medium. However, the rate of ethylene polymerization to form high molecular weight, normally solid polymers is preferably not such as to yield said solid polymers in quantities which substantially exceed the solubility thereof in said liquid reaction medium under the reaction conditions, usually up to about 5-7 weight percent, exclusive of the amounts of polymeric products which are selectively adsorbed by the catalyst. Although ethylene concentrations above 10 weight percent in the liquid reaction medium may be used, solutions of ethylene polymer above 5-10% in the reaction medium become very viscous and difficult to handle and severe cracking or spalling of the catalyst particles or fragments may occur, resulting in catalyst carry-over as fines with the solution of polymerization products and extensive loss of catalyst from the reactor.

In batch operations, operating periods between onehalf and about 20 hours are employed and the reaction autoclave is charged with ethylene as the pressure falls as a result of the olefin conversion reaction.

The olefin charging stocks can be polymerized in the gas phase and in the absence of a liquid reaction medium by contact with the catalyst. Upon completion of the desired polymerization reaction it is then possible to treat the catalyst for the recovery of the solid polymerization products, for example by extraction with suitable solvents. However, in the interests of obtaining increased rates of olefin conversion and of continuously removing solid conversion products from the catalyst, it is much preferred to etfect the conversion of the olefin in the presence of suitable liquid reaction media. The liquid reaction medium may also be employed as a means of contacting the olefin with catalyst by preparing a solution of the olefin feed stock in the liquid reaction medium and contacting the resultant solution with the polymerization catalyst.

The liquid reaction medium functions as a solvent to remove some of the normally solid product from the catalyst surface.

Various classes of hydrocarbons or their mixtures which are liquid under the polymerization conditions of the present process can be employed. Members of the aromatic hydrocarbon series, particularly the mononuclear aromatic hydrocarbons, viz., benzene, toluene. xylenes, mesitylene and xylene-p-cymene mixtures can be employed. Tetrahydronaphthalene can also be employed. In addition, we may employ such aromatic hydrocarbons as ethylbenzene, isopropylbenzene, sec-butylbenzene, t-butylbenzene, ethyltoluene, ethylxylenes, hemimellitene, pseudocumene, prehnitene, isodurene, diethylbenzenes, isoamylbenzene and the like. Suitable aromatic hydrocarbon fractions can be obtained by the selective extraction of aromatic naphthas, from hydroforming operations as distillates or bottoms, from cycle stock fractions of cracking operations, etc.

We may also employ certain alkyl naphthalenes which are liquid under the polymerization reaction conditions, for example, l-methylnaphthalene, 2-isopropylnaphthalene, I-n-amylnaphthalene and the like, or commercially produced fractions containing these hydrocarbons.

Certain classes of aliphatic hydrocarbons can also be hydrocarbon reaction medium in Thus, we may employ various saturated hydrocarbons (alkanes and cycloalkanes) which are liquid under the polymerization reaction conditions and which do not crack substantially under the reaction the present process.

conditions. Either pure alkanes or cycloalkanes or commercially available mixtures, freed of'catalyst poisons, may be employed. For example, we mayemploy straight run naphthas or kerosenes containing alkanes and cycloalkanes. Specifically, we may employ liquid or liquefied alkanes such as n-pentane, n-hexane, 2,3-dimethylbutane, n-octane, iso-octane (2,2,4-trimethylpentane), n-decane, n-dodecane, cyclohexane, methylcyclohexane, dimethylcyclopentane, ethylcyclohexane, decalin, methyldecalins, dimethyldecalins and the like.

We may also employ a liquid hydrocarbon, reaction medium comprising liquid olefins,..e.g., n-hexenes,-cyclohexene, octenes, hexadecenes and'the like.

The normally solid polymerization products which are retained on the catalyst surface or grease-like ethylene polymers may themselves function to some extent as a liquefied hydrocarbon reaction medium, but. it is highly desirable to add a viscosity-reducing hydrocarbon, such as those mentioned above, thereto in the reaction zone.

The liquid hydrocarbon reaction medium shouldbe freed of poisons before use in thepresent invention by acid treatment, e.g., with anyhydrous p-toluenesulfonic acid, sulfuric acid, or by equivalent treatments,v for example with aluminum halides, orother Friedel-Crafts catalysts, maleic anhydride, calcium, calcium hydride, sodium or other alkali metals, alkali metal hydrides, lithium aluminum hydride, hydrogen and hydrogenation catalysts (hydrofining), filtration through a column of vcopper grains or 8th group metal, etc., or by combinations of such treatments.

We have purified C.P. xylenes by refluxing with a mixture of 8'weight percent M00 on A1 0 catalyst and LiAlH (50 cc. xylene-1 g. catalyst-02 g. LiAlH at atmospheric pressure, followed by distillation of the xylenes. Still more effective purification of solvent can be achieved by heating it to about.2252507 vC. with either sodium and hydrogen or NaH plus 8 weight percent MoO -Al O catalyst in a pressure vessel.

Temperature control during the course of the ethylene conversion process can be readily accomplished owing to the presence in-the reaction-zoneofa" large liquid mass having relatively high heatcapacity. The liquid hydrocarbon reaction medium can be cooled by heat exchange inside or outside the reaction zone.

When solvents such as xylenes are employed alkylation thereof by ethylene can occur under the reaction conditions. The alkylate is removed with grease in the present process, can be separated therefrom by fractional distillation and can, if desired, be returned to the polymerization zone.

The following specific examples are introduced in order to illustrate but not unduly to limit our invention. The exemplary operations were effected in 250 cc. capacity stainless steel pressure vessels provided with a magnetically-actuated stirring device which was reciprocated through the liquid in the vessel in order to obtain good contacting of the ethylene and catalyst components.

Example 1 The autoclave was charged with 100 cc. of dehydrated and decarbonated toluene which was freshly distilled, 0.2 g. of lithium aluminum hydride and l g. of nickel catalyst. This catalyst was prepared by evaporating a 10% nickel nitrate solution while stirring an activated coconut charcoal, 8-14 mesh per inch, until all the nickel nitrate was deposited on the support. The catalyst was dried at 110 C. and then heated in steam at atmospheric pressure while the temperature was gradually raised from 100' C. to 290 C. Decomposition of the nickel nitrate on the charcoal occurred to form a catalyst comprising essentially NiO on charcoal. The nickel catalyst contained 5 weight percent of nickel. The contents of the autoclave were heated with stirring to 124 C. and ethylene was then injected to a partial pressure of 835 p.s.i. Reaction was continued for 21 hours.

Upon. conclusion of the" reaction the reactor contents were cooled to room temperature, the pressure was vented to atmospheric pressure and the nickel catalyst containing adsorbed polyethylenes was removed and extracted with hot xylenes. The hot xylenes solution was cooled to room temperature to precipitate a tough, resinous ethylene polymer which was filtered and the filtrate was evaporated to leave a grease-like solid polyethylene. residue. The reaction yielded 2.6 g. per g. of. the nickel catalyst of a solid polymer of ethylene having a' specific gravity (24/4 C.) ofv 0.953, Williams plasticity of 40.4 and melt viscosity of 2.4 10 (method of Dienes'rand Klemm, J. Appl. Phys., 17, 458-71 (1946)). Theayield of solid grease-like polyethylenes was 1.1 g. per gzofthe nickel catalyst.

In sharp contrast to the above results are the results which were obtained in the following experiment in which no promoter was employed. The charge to the reactor was the same as in the above-example but no promoter was included and it was found that the yield of solid polyethylenes was only 0.01 g. per g. and the yield of solid grease-like polyethylenes was only 0.05 g. per g. of the solid catalyst. The reaction, period was 20 hours. 7

In another control runthe reactor was charged with cc. of the purified toluene, 2g. of the 5% nickel oxidecharcoal catalyst, heated with stirring to 131 C. and then .pressured with ethylene to a partial pressure of 910 p.s.i. The operating period was 20.5 hours. The reaction yielded only a trace of solid polyethylenes and 0.25 cc. of a liquid polymer per gram of the nickel catalyst.

To determine whether or not LiAlI-L, is itself a catalyst under the conditions We usually employ for the polymerization of ethylene, 1.0 g. of LiAlH; and 50cc. benzene were charged to a reaction bomb. The bomb was heated to C. and 900 p.s.i. of ethylene was charged to the bomb. The temperature was gradually increased to 175 C. at which point a definite pressure drop was obtained. No further pressure drop was obtained until the temperature was raised to 240250 C. The rate of polymerization was rapid and increased linearly to a pressure. drop of 1520 p.s.i. at which time the run was stopped. The run yielded 18.6 g. of products. The overall analysis of the products as determined by mass spectrometer and fractional distillation was as follows: C 22%; C 30%; a 10 12, 14: 16+ N0 solid polymer was formed. By infra-red analysis the C fraction was found to be butene-l. The C fraction was 3.6% hexanes and 96.4% hexenes. The latter were present in the proportion of 40% l-hexene, 10% 2-ethyl-.

Example 2 The reactor was charged with 100 cc. of purified toluene, 0.5 g. of NaAll-I and l g. of nickel catalyst having the same composition and prepared by the same method as the nickel catalyst of Example 1. The contents of the reactor were heated with stirring to C. and ethylene was then introduced to a partial pressure of 830 p.s.i. Reaction was continued for 20 hours. The reaction products were worked up as in Example 1. The yield of solid polyethylenes was 0.20 g. per g. of nickel catalyst. The reaction also yielded 1.25 g. of solid grease-like polyethylenes per gram of the nickel catalyst.

Example 3 The process of Example 2 is repeated but the NaAlI-Is, is replaced by 0.65 g. of KAlH The products are worked up as before to produce solid polymers of ethylene.

In large scale operations the flow-scheme shown in the E. Field and M. Feller application, Serial No. 324,608, filed December 6, 1952, may be employed.

, The polymers produced by the process of this invention can be subjected to such after-treatment as may be desired to fit them for particular uses or to impart desired properties. Thus, the polymers can-be extruded, mechanically milled, filmed or cast, or converted to sponges or latices. Antioxidants, stabilizers, fillers, extenders, plasticizers, pigments, insecticides, fungicides, etc. can be incorporated in the polyethylenes and/or in by-product alkylates or greases. The polyethylenes may be employed as coating materials, binders, etc.

i The polymers produced by the process of the present invention, especially the polymers having high specific viscosities, can be blended with the lower molecular weight polyethylenes to impart stiffness or flexibility or other desired properties thereto. The solid resinous products pro duced by the process of the present invention can, likewise, be blended in any desired proportions with hydrocarbon oils, waxes such as paraflin or petrolatum waxes, with ester waxes, with high molecular weight polybutylenes, and with other organic materials. Small proportions between about .01 and about 1 percent of the .various polymers of ethylene produced by the process of the present invention can be dissolved or dispersed in hydrocarbon lubricating oils to increase V1. and to decrease oil consumption when the compounded Oils are employed in motors; larger amounts of polyethylenes may be compounded with oils of various kinds and for various purposes.

The products can be employed in small proportions to substantially increase the viscosity of fluent liquid hydrocarbon oils and as gelling agents for such oils.

The polymers produced by the present process can be subjected to chemical modifying treatments, such as halogenation, halogenation followed by dehalogenation, sulfohalogenation by treatment with sulfuryl chloride or a mixture of sulfur dioxide and chlorine, sulfonation, and other reactions to which hydrocarbons may be subjected.

Having thus described our invention, what We claim is:

1. In a process for the preparation of a normally solid polymer, the steps of exposing ethylene to a catalytic mixture prepared by admixing an alkali metal aluminum hydride with nickeloxide in a proportion between about 0.1 and about 20 weight percent, calculated as elemental nickel, supported upon an activated carbon, eiiecting said exposure at an efiective polymerization temperature between about 25 C. and about 250 C., and recovering a normally solid polymer thus produced.

, v2. In a process for the preparation of a normally solid polymer, the steps of exposing ethylene to a catalytic mixture prepared by admixing an alkali metal aluminum hydride with nickel oxide in a proportion between about 0.1 and about 20 weight percent, calculated as elemental nickel, supported upon an activated carbon, effecting said exposure in the presence of a liquid hydrocarbon reaction medium at an effective polymerization temperature between about 25 C. and about 250 C., and recovering a normally solid polymer thus produced.

3.. The process of claim 2 wherein said hydride is lithium aluminum hydride.

' 4. The process of claim 2 wherein said hydride is sodium aluminum hydride.

5. The process of'claim 2 wherein said hydride is potassium aluminum hydride.

6. A process for the productiton of a normally solid polymer, which process comprises exposing ethylene and a liquid hydrocarbon reaction medium at an effective poly- 'merization temperature between about 25 C. and about 250 C. to a catalytic mixture prepared by admixing an alkali metal aluminum hydride in a weight ratio between about 0.01 and about 1. with nickel oxide in a proportion between about'0.l and about 20 weight percent, calculatedv as elemental nickel, supported upon an activated coconut charcoal, and'recovering a normally solid polymer thus produced.

7. The process of claim 6 wherein the polymerization temperature is between about C. and about C.

8. The process of claim 6 wherein said liquid hydrocarbon reaction medium is a monocyclic aromatic hydrocarbon.

9. The process of claim 6 wherein said liquid hydrocarbon reaction medium is a saturated hydrocarbon.

10. The process of claim 6 wherein said hydride is lithium aluminum hydride.

11 The process of claim 6 wherein said hydride is sodium aluminum hydride.

12. The process of claim 6 wherein said hydride is potassium aluminum hydride.

References Cited in the file of this patent UNITED STATES PATENTS 2,658,059 Peters et al. Nov. 3, 1953 2,691,647 Field et al Oct. 12, 1954 2,692,261 Peters et al Oct. 19, 1954 2,767,160 Field et a1 Oct. 16, 1956 

1. IN A PROCESS FOR THE PREPARATION OF A NORMALLY SOLID POLYMER, THE STEPS OF EXPOSING ETHYLENE TO A CATAYTIC MIXTURE PREPARED BY ADMIXING AN ALKALI METAL ALUMINUM HYDRIDE WITH NICKEL OXIDE IN A PROPORTION BETWEEN ABOUT 0.1 AND ABOUT 20 WEIGHT PERCENT,CALCULATED AS ELEMENTAL NICKEL, SUPPORTED UPON AN ACTIVATED CARBON, EFFECTING SAID EXPOSURE AT AN EFFECTIVE POLYMERIZATION TEMPERATURE BETWEEN ABOUT 25* C. AND ABOUT 250* C., AND RECOVERING A NORMALLY SOLID POLYMER THUS PRODUCED. 